EP1305354B1 - Verfahren zur herstellung eines polyurethanmaterials - Google Patents

Verfahren zur herstellung eines polyurethanmaterials Download PDF

Info

Publication number
EP1305354B1
EP1305354B1 EP01965034A EP01965034A EP1305354B1 EP 1305354 B1 EP1305354 B1 EP 1305354B1 EP 01965034 A EP01965034 A EP 01965034A EP 01965034 A EP01965034 A EP 01965034A EP 1305354 B1 EP1305354 B1 EP 1305354B1
Authority
EP
European Patent Office
Prior art keywords
weight
isocyanate
polyisocyanate
reactive
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01965034A
Other languages
English (en)
French (fr)
Other versions
EP1305354A1 (de
Inventor
Gerhard Jozef Bleys
Eric Huygens
Anja Vanhalle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman International LLC
Original Assignee
Huntsman International LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman International LLC filed Critical Huntsman International LLC
Priority to SI200130454T priority Critical patent/SI1305354T1/sl
Priority to EP01965034A priority patent/EP1305354B1/de
Publication of EP1305354A1 publication Critical patent/EP1305354A1/de
Application granted granted Critical
Publication of EP1305354B1 publication Critical patent/EP1305354B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups

Definitions

  • the present invention is related to a process for preparing a polyurethane material. More specifically the present invention is related to a process for preparing a polyurethane material using a polyoxyethylene polyoxypropylene polyol having a high oxyethylene content and a polyisocyanate having a high 4,4'-diphenylmethane diisocyanate (4,4'-MDI) content.
  • polyurethane materials having a high hardblock content from polyols having a high oxyethylene content, polyisocyanates comprising at least 85% by weight of 4,4'-MDI or a variant thereof and water has been disclosed in WO 98/00450.
  • the materials made are elastomers and hence show a glass transition temperature of less than 25°C.
  • EP 608626 it has been disclosed in EP 608626 to produce shape memory polyurethane foams by reacting a polyisocyanate comprising a high amount of 4,4'-MDI and a polyol with a high oxyethylene content with water.
  • the foams have a glass transition temperature above 25°C; the amounts of chain extender and cross-linker used are relatively low, leading to products with a limited hard-block content giving products which are not as stiff as sometimes desirable.
  • a polyurethane material which has a glass transition temperature of at least 25°C and shows a high stiffness at a given density.
  • the material obtained shows less surface defects (improved mixing, less bubbles) and a relatively high "ductility" (i.e. not brittle).
  • the combination of ingredients used for making these materials show a good wetting of fibrous materials and in particular of glass fibres which makes the process particularly suitable for reaction injection moulding (RIM), especially for reinforced RIM (RRIM) and structural RIM(SRIM).
  • the present invention is concerned with a process for preparing a polyurethane material having no glass transition temperature below 25°C, which process comprises reacting a polyisocyanate and an isocyanate-reactive composition, optionally in the presence of water in an amount of less than 5% by weight on the below isocyanate-reactive composition, wherein the reaction is conducted at an isocyanate index of 80 to 140, the polyisocyanate consists of a) 80-100% by weight of diphenylmethane diisocyanate comprising at least 40%, preferably at least 60% and most preferably at least 85% by weight of 4,4'-diphenylmethane diisocyanate and/or a variant of said diphenylmethane diisocyanate which variant is liquid at 25°C and has an NCO value of at least 20% by weight (polyisocyanate a), and b) 20-0% by weight of another polyisocyanate (polyisocyanate b), and wherein the isocyanate-reactive
  • the materials prepared according to the present invention have no glass transition temperature, Tg, below 25°C and preferably not below 60°C.
  • the Tg is defined as the temperature at which the tan ⁇ curve reaches its maximum value as measured by Dynamic Mechanical Thermal Analysis (DMTA) at 1 Hz and a heating rate of 3°C/min).
  • DMTA Dynamic Mechanical Thermal Analysis
  • the polyisocyanate a) is selected from 1) a diphenylmethane diisocyanate comprising at least 40%, preferably at least 60% and most preferably at least 85% by weight of 4,4'-diphenylmethane diisocyanate and the following preferred variants of such diphenylmethane diisocyanate : 2) a carbodiimide and/or uretonimine modified variant of polyisocyanate 1), the variant having an NCO value of 20% by weight or more; 3) a urethane modified variant of polyisocyanate 1), the variant having an NCO value of 20% by weight or more and being the reaction product of an excess of polyisocyanate 1) and of a polyol having an average nominal hydroxyl functionality of 2-4 and an average molecular weight of at most 1000; 4) a prepolymer having an NCO value of 20% by weight or more and which is the reaction product of an excess of any of the aforementioned polyisocyanates 1-3) and of a polyiso
  • Polyisocyanate 1 comprises at least 40% by weight of 4,4'-MDI.
  • Such polyisocyanates are known in the art and include pure 4,4'-MDI and isomeric mixtures of 4,4'-MDI and up to 60% by weight of 2,4'-MDI and 2,2'-MDI.
  • 2,2'- MDI in the isomeric mixtures is rather at an impurity level and in general will not exceed 2% by weight, the remainder being 4,4'-MDI and 2,4'-MDI.
  • Polyisocyanates as these are known in the art and commercially available; for example SuprasecTM MPR ex Huntsman Polyurethanes, which is a business of Huntsman International LLC (who owns the Suprasec trademark).
  • the carbodiimide and/or uretonimine modified variants of the above polyisocyanate 1) are also known in the art and commercially available; e.g. Suprasec 2020, ex Huntsman Polyurethanes.
  • Urethane modified variants of the above polyisocyanate 1) are also known in the art, see e.g. The ICI Polyurethanes Book by G. Woods 1990, 2 nd edition, pages 32-35.
  • Aforementioned prepolymers of polyisocyanate 1) having an NCO value of 20% by weight or more are also known in the art.
  • the polyol used for making these prepolymers is selected from polyester polyols and polyether polyols and especially from polyoxyethylene polyoxypropylene polyols having an average nominal functionality of 2-4, an average molecular weight of 2500-8000, and preferably an hydroxyl value of 15-60 mg KOH/g and preferably either an oxyethylene content of 5-25% by weight, which oxyethylene preferably is at the end of the polymer chains, or an oxyethylene content of 50-90% by weight, which oxyethylene preferably is randomly distributed over the polymer chains.
  • Mixtures of the aforementioned polyisocyanates may be used as well, see e.g. The ICI Polyurethanes Book by G. Woods 1990, 2 nd edition pages 32-35.
  • the other polyisocyanate b) may be chosen from aliphatic, cycloaliphatic, araliphatic and, preferably, aromatic polyisocyanates, such as toluene diisocyanate in the form of its 2,4 and 2,6-isomers and mixtures thereof and mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof having an isocyanate functionality greater than 2 known in the art as "crude” or polymeric MDI (polymethylene polyphenylene polyisocyanates). Mixtures of toluene diisocyanate and polymethylene polyphenylene polyisocyanates may be used as well.
  • aromatic polyisocyanates such as toluene diisocyanate in the form of its 2,4 and 2,6-isomers and mixtures thereof and mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof having an isocyanate functionality greater than 2 known in the art as "crude” or
  • the amount of these polyols in the prepolymers compared to the total amount of polyols having such molecular weight used in making the polyurethane material is preferably less than 50% and more preferably less than 30% by weight.
  • Polyol 1) having a high EO content and a high primary hydroxyl content is selected from those having an EO content of 50-100% and preferably 75-100% by weight calculated on the weight of the polyether polyol and a primary hydroxyl content of 70-100% and preferably of 80-100 % calculated on the number of primary and secondary hydroxyl groups in the polyol.
  • polyether polyols may contain other oxyalkylene groups like oxypropylene and/or oxybutylene groups. These polyols have an average nominal functionality of 3-8 and more preferably of 3-6, an average equivalent weight of 200-2000 and preferably of 200-1800 and a molecular weight of 600-8000, preferably of 600-5000. As long as there are sufficient oxyethylene groups at the end of the polymer chains so as to meet the requirement of the primary hydroxyl content the distribution of the oxyethylene and other oxyalkylene groups (if present) over the polymer chains may be of the type of a random distribution, a block copolymer distribution or a combination thereof. Mixtures of polyols may be used.
  • the isocyanate-reactive chain extenders which have a functionality of 2, may be selected from amines, amino-alcohols and polyols; preferably polyols are used. Further the chain extenders may be aromatic, cycloaliphatic, araliphatic and aliphatic; preferably aliphatic ones are used. The chain extenders have a molecular weight of 500 or less.
  • aliphatic diols having a molecular weight of 62-500, such as ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,2-hexanediol, 3-methylpentane-1,5-diol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol and tripropylene glycol, and propoxylated and/or ethoxylated products thereof.
  • ethylene glycol 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-
  • the cross-linkers are isocyanate-reactive compounds having an average molecular weight 500 or less and a functionality of 3-8.
  • examples of such cross-linkers are glycerol, trimethylolpropane, pentaerythritol, sucrose, sorbitol, mono-, di- and triethanolamine, ethylenediamine, toluenediamine, diethyltoluene diamine, polyoxyethylene polyols having an average nominal functionality of 3-8 and an average molecular weight of 500 or less like ethoxylated glycerol, trimethylol propane, pentaerythritol, sucrose and sorbitol having said molecular weight, and polyether diamines and triamines having an average molecular weight below 500; most preferred cross-linkers are the polyol cross-linkers.
  • the amount of chain extenders and/or cross-linkers used is such that the hard block ratio is 0.60 or more and preferably at least 0.65.
  • the other isocyanate-reactive compounds which may be used in an amount of 0-20% by weight and preferably of 0-10% by weight, may be selected from polyether polyamines, polyester polyols and polyether polyols (different from the above described ones) having a molecular weight of more than 500 and in particular from such other polyether polyols, which may be selected from polyoxyethylene polyols, polyoxypropylene polyols, polyoxyethylene polyoxypropylene polyols having an oxyethylene content of less than 50% by weight and polyoxyethylene polyoxypropylene polyols having a primary hydroxyl content of less than 70%.
  • Preferred polyoxyethylene polyoxypropylene polyols are those having an oxyethylene content of 5-30% and preferably 10-25% by weight, wherein all the oxyethylene groups are at the end of the polymer chains (so-called EO-capped polyols) and those having an oxyethylene content of 60-90% by weight and having all oxyethylene groups and oxypropylene groups randomly distributed and a primary hydroxyl content of 20-60%, calculated on the number of primary and secondary hydroxyl groups in the polyol.
  • these other polyether polyols have an average nominal functionality of 2-6, more preferably 2-4 and an average molecular weight of 2000-10000, more preferably of 2500-8000.
  • the other isocyanate-reactive compounds may be selected from polyesters, polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins or polysiloxanes.
  • Polyester polyols which may be used include hydroxyl-terminated reaction products of dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol or cyclohexane dimethanol or mixtures of such dihydric alcohols, and dicarboxylic acids or their ester-forming derivatives, for example succinic, glutaric and adipic acids or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof.
  • Polyesteramides may be obtained by the inclusion of aminoalcohols such as ethanolamine in polyesterification mixtures.
  • Polythioether polyols which may be used, include products obtained by condensing thiodiglycol either alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids.
  • Polycarbonate polyols which may be used include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or teraethylene glycol with diaryl carbonates, for example diphenyl carbonate, or with phosgene.
  • Polyacetal polyols which may be used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerising cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols.
  • the other isocyanate-reactive compounds may be used as well.
  • the other isocyanate-reactive compounds are polyols selected from the above preferred ones.
  • the polyols may comprise dispersions or solutions of addition or condensation polymers in polyols of the types described above.
  • modified polyols often referred to as "polymer polyols" have been fully described in the prior art and include products obtained by the in situ polymerisation of one or more vinyl monomers, for example styrene and/or acrylonitrile, in the above polyether polyols, or by the in situ reaction between a polyisocyanate and an amino- and/or hydroxy-functional compound, such as triethanolamine, in the above polyol.
  • Polyoxyalkylene polyols containing from 1 to 50% of dispersed polymer are particularly useful. Particle sizes of the dispersed polymer of less than 50 microns are preferred.
  • polyether polyols having a low level of unsaturation have been described. These developments have made it possible to use polyether polyols at the higher end of the molecular weight range since such polyols can now be prepared with an acceptably low level of unsaturation. According to the present invention polyols having a low level of unsaturation may be used as well.
  • catalysts enhancing the formation of urethane bonds like tin catalysts like tin octoate and dibutyltindilaurate, tertiary amine catalysts like triethylenediamine and imidazoles like dimethylimidazole and other catalysts like maleate esters and acetate esters; surfactants; foam stabilisers like siloxane-oxyalkylene copolymers; fire retardants; smoke suppressants; UV-stabilizers; colorants; microbial inhibitors; organic and inorganic fillers and internal mould release agents. Further external mould release agents may be used.
  • a particularly preferred class of catalyst is an alkali metal or alkaline earth metal carboxylate salt.
  • the catalyst may be a salt of any metal of Groups IA and IIA of the Periodic Table but in general the alkali metal salts are preferred like potassium and sodium salts, especially the potassium salts. If desired mixtures of such salts may be used like a mixture of a potassium and a sodium salt.
  • a catalytically effective amount of the salt will usually be in the range of 0.1 to 10, preferably 0.2-5 parts by weight per 100 parts by weight of reactants.
  • other polyurethane catalysts may be used together with the carboxylate salt catalysts, like the generally known tertiary amine catalysts and tin catalysts, it is preferred that the materials are made in the absence of other catalysts in particular in the absence of tertiary amine and tin catalysts.
  • the carboxylate may be selected from aliphatic carboxylates having 2-10 carbon atoms like acetate, hexanoate, 2-ethylhexanoate and octanoate.
  • carboxylate may be selected from those having the formula R-E-A-COO- wherein A is a hydrocarbon diradical having 1-6 preferably 1-3 carbon atoms; E is -O- or and R is X-R 1 -(OR 2 ) n - wherein X is CH 3 - or OH-, R1 is a hydrocarbon diradical having 1-8 and preferably 1-4 carbon atoms, R2 is a hydrocarbon diradical having 2-4 and preferably 2 or 3 carbon atoms and n is 0 to 10, preferably 0-5.
  • R 1 may be selected from those diradicals mentioned for A and from radicals obtained by removing two hydrogen atoms from e.g. butane, pentane, hexane and octane.
  • the most preferred radicals for R 1 are methylene, ethylene, trimethylene, tetramethylene and propylene.
  • R 2 may be selected from ethylene, trimethylene, tetramethylene, ethylethylene and propylene. Most preferred groups are ethylene and propylene. Such catalysts and their preparation are known as such, see EP 294161, EP 220697 and EP 751114.
  • catalysts are sodium acetate, potassium acetate, potassium hexanoate, potassium 2-ethylhexanoate, potassium ethoxyacetate, sodium ethoxyacetate, the potassium salt of the hemi-ester of maleic acid and ethoxyethane, ethoxyethoxyethane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, methanol, ethanol, propanol or butanol and the potassium salt of the hemi-ester of such hydroxy containing compounds with malonic, succinic, glutaric, adipic or fumaric acid. Mixtures of these catalysts may be used as well.
  • the polyurethane material may be a solid or blown (microcellular) material.
  • Microcellular materials are obtained by conducting the reaction in the presence of a blowing agent, like hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, gases like N 2 and CO 2 , and water. Most preferably water is used as the blowing agent.
  • the amount of blowing agent will depend on the desired density.
  • the amount of water will be less than 5, preferably less than 3 and most preferably less than 1% by weight; calculated on the weight of the isocyanate-reactive composition.
  • the reaction to prepare the material is conducted at an NCO index of 80-140 and preferably of 90-130 and most preferably of 90-110.
  • the density of the materials is higher than 25 kg/m 3 and preferably higher than 50 kg/m 3 and more preferably higher than 500 kg/m 3 .
  • the materials are preferably made in a mould.
  • the process may be conducted in any type of mould known in the art. Examples of such moulds are the moulds commercially used for making polyurethane shoe soles, automotive parts, like arm-rests, door panels and back-shelves.
  • the reaction is conducted in a closed mould.
  • the ingredients used for making the material are fed into the mould at a temperature of from ambient temperature up to 80°C and preferably up to 70°C, the mould being kept at a temperature of from ambient temperature up to 80°C and preferably up to 70°C during the process.
  • Demoulding time is relatively short despite the fact that preferably no isocyanate-reactive compounds, containing amine groups, are used; depending on the amount of catalyst demould times may be below 10 minutes, preferably below 5 minutes, more preferably below 3 minutes and most preferably below 1 minute.
  • the moulding process may be conducted according to the reaction injection moulding (RIM) process and the cast moulding process. In particular the process is conducted according to RRIM and SRIM process.
  • the isocyanate-reactive ingredients are pre-mixed, optionally together with the optional ingredients, before being brought into contact with the polyisocyanate.
  • the materials according to the invention are particularly suitable for use in applications where high stiffness, non-brittle, high impact resistant and low density materials are desirable, like shoe soles and automotive parts like arm-rests, doorpanels, back-shelves and sun visors.
  • Example 1 Caradol SA 3602 26.81 - Polyol 1 - 26.89 1,4-butanediol 15.11 12.78 DABCO EG 0.3 0.1 Polyisocyanate 57.78 60.23 Hardblock ratio, % 72.9 73 Density, kg/m3 (DIN 53420) 929 957 Shore D (DIN 53505) 70 77 Tg, °C (Ihz, 3°C/min DMTA) 70 87
  • the polyols used were not dried before use and likely have contained a minor amount of residual water, reason why a density of 929 and 957 kg/m 3 was obtained.
  • CaradolTM SA 3602 Ex Shell is a polyol having a nominal hydroxyl functionality of 3, an OH-value of 36 mg KOH/g, an oxyethylene content of about 77% by weight and a primary hydroxy content of about 90%.
  • DABCO EG is an amine catalyst from AirProducts.
  • the polyisocyanate is a polyisocyanate having an NCO value of 26.2% by weight and which is a mixture of 1) a polyisocyanate made by reacting 42.55 pbw of MDI comprising more than 95% by weight of 4,4'-MDI and 5.05 pbw of a mixture of tripropylene glycol, propylene glycol and 1,3-butanediol (59/18.79/22.21, /w/w/w) and of 2) Suprasec 2020 (52.4 pbw) (a uretonimine-modified MDI from a polyisocyanate comprising more than 95% w 4,4'-MDI having an NCO value of 29.5% by weight ex Huntsman Polyurethanes).
  • Polyol 1 is a sorbitol initiated polyoxyethylene polyol having an OH value of 187 mg KOH/g and a molecular weight of 1800.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (5)

  1. Verfahren zur Herstellung eines Polyurethanmaterials, das keine Glasübergangstemperatur von unterhalb von 25°C hat, wobei das Verfahren das Umsetzen eines Polyisocyanats und einer Isocyanat-reaktiven Zusammensetzung, ggf. in Gegenwart von Wasser in einer Menge von wenigstens 5 Gew.% bezogen auf die Isocyanat-reaktive Zusammensetzung unten, umfasst, wobei die Reaktion bei einem Isocyanat-Index von 80 bis 140 durchgeführt wird, das Isocyanat aus a) 80-100 Gew.% Diphenylmethandiisocyanat aus wenigstens 40 Gew.% 4,4'-Diphenylmethandiisocyanat und/oder einer Variante des Diphenylmethandiiisocyanats, wobei die Variante bei 25°C flüssig ist und einen NCO-Wert von wenigstens 20 Gew.% hat (Polyisocyanat a), und b) 20-0 Gew.% eines weiteren Polyisocyanats (Polyisocyanat b) besteht, und wobei die Isocyanat-reaktive Zusammensetzung aus a) 80-100 Gew.% eines Polyetherpolyols mit einer zahlenmittleren Funktionalität von 3-8, einem Durchschnittsäquivalentgewicht von 200-2000, einem Durchschnittsmolekulargewicht von 60-8000, einem Oxyethylengehalt (EO) von 50-100 Gew.% und einem primären Hydroxylgehalt von 70-100%, bezogen auf die Anzahl der primären und sekundären Hydroxylgruppen im Polyol, b) einem Isocyanat-reaktiven Kettenverlängerer und/oder Vernetzer in einer solchen Menge, dass das Hartblockverhältnis 0,60 oder mehr ist und c) 20-0 Gew.% eines oder mehrerer Isocyanat-reaktiver Verbindungen einschließlich Wasser besteht, wobei die Menge an Polyol a) und Isocyanat-reaktiver Verbindung c) auf die Gesamtmenge dieses Polyols a) und Verbindung c) bezogen berechnet ist.
  2. Verfahren nach Anspruch 1, wobei das Material keine Glasübergangstemperatur von unterhalb von 60°C hat, das Diphenylmethan-Diisocyant wenigstens 85 Gew.% an 4,4'-Diphenylmethan-Diisocyanat und/oder einer Variante dieses Diisocyanats, wobei die Variante bei 25°C flüssig ist und einen NCO-Wert von wenigstens 20 Gew.% hat, umfasst, der Oxyethylengehalt im Polyetherpolyol 75-100 Gew.% ist und das Hartblockverhältnis wenigstens 0,65 ist.
  3. Verfahren nach den Ansprüchen 1-2, wobei das Material eine Dichte von mehr als 500 kg/m3 besitzt.
  4. Verfahren nach Anspruch 1-3, wobei der Isocyanatindex 90-110 ist.
  5. Material, hergestellt nach dem Verfahren der Ansprüche 1-4.
EP01965034A 2000-08-01 2001-06-25 Verfahren zur herstellung eines polyurethanmaterials Expired - Lifetime EP1305354B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
SI200130454T SI1305354T1 (sl) 2000-08-01 2001-06-25 Postopek za pripravo poliuretanskega materiala
EP01965034A EP1305354B1 (de) 2000-08-01 2001-06-25 Verfahren zur herstellung eines polyurethanmaterials

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00116582 2000-08-01
EP00116582A EP1178063A1 (de) 2000-08-01 2000-08-01 Verfahren zur Herstellung eines Polyurethanmaterials
PCT/EP2001/007199 WO2002010249A1 (en) 2000-08-01 2001-06-25 Process for preparing a polyurethane material
EP01965034A EP1305354B1 (de) 2000-08-01 2001-06-25 Verfahren zur herstellung eines polyurethanmaterials

Publications (2)

Publication Number Publication Date
EP1305354A1 EP1305354A1 (de) 2003-05-02
EP1305354B1 true EP1305354B1 (de) 2005-11-02

Family

ID=8169413

Family Applications (2)

Application Number Title Priority Date Filing Date
EP00116582A Withdrawn EP1178063A1 (de) 2000-08-01 2000-08-01 Verfahren zur Herstellung eines Polyurethanmaterials
EP01965034A Expired - Lifetime EP1305354B1 (de) 2000-08-01 2001-06-25 Verfahren zur herstellung eines polyurethanmaterials

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP00116582A Withdrawn EP1178063A1 (de) 2000-08-01 2000-08-01 Verfahren zur Herstellung eines Polyurethanmaterials

Country Status (20)

Country Link
US (1) US6806342B2 (de)
EP (2) EP1178063A1 (de)
JP (1) JP4953544B2 (de)
KR (1) KR100730670B1 (de)
CN (1) CN100369948C (de)
AR (1) AR030089A1 (de)
AT (1) ATE308576T1 (de)
AU (2) AU8577701A (de)
BR (1) BR0112898B1 (de)
CA (1) CA2417267C (de)
CZ (1) CZ298395B6 (de)
DE (1) DE60114633T2 (de)
ES (1) ES2247161T3 (de)
MX (1) MXPA03000667A (de)
PL (1) PL365156A1 (de)
RU (1) RU2268270C2 (de)
SI (1) SI1305354T1 (de)
TW (1) TWI257934B (de)
WO (1) WO2002010249A1 (de)
ZA (1) ZA200300295B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3898745B1 (de) * 2018-12-19 2023-08-30 Basf Se Polyurethan-weichschäume mit verbesserten dauergebrauchseigenschaften

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1263831B1 (de) * 2000-02-14 2005-11-02 Huntsman International Llc Verfahren zur herstellung eines flexiblen polyurethanschaums
US20050131095A1 (en) * 2002-08-02 2005-06-16 Jianming Yu Novel polyols
RU2372358C2 (ru) * 2003-06-12 2009-11-10 Хантсмэн Интернэшнл Ллс Способ получения полиизоциануратполиуретанового материала
ES2405277T3 (es) * 2004-10-25 2013-05-30 Dow Global Technologies Inc. Respaldos de alfombras de poliuretano realizados con polioles de poliéster hidroximetilados
ATE491734T1 (de) * 2005-10-13 2011-01-15 Huntsman Int Llc Verfahren zur herstellung eines polyisocyanuratpolyurethanmaterials
CA2625689C (en) * 2005-10-13 2013-07-09 Huntsman International Llc Process for preparing polyisocyanurate polyurethane material
EP1989242B1 (de) * 2006-02-21 2010-07-21 Huntsman International Llc Herstellungsverfahren für einen polyisocyanuratverbund
MX2008016002A (es) 2006-06-14 2009-01-16 Huntsman Int Llc Panel compuesto.
CN101631810B (zh) 2006-12-29 2013-07-24 江森自控科技公司 聚氨酯泡沫组成、产品及方法
US20090035350A1 (en) 2007-08-03 2009-02-05 John Stankus Polymers for implantable devices exhibiting shape-memory effects
WO2009101027A1 (en) 2008-02-14 2009-08-20 Huntsman International Llc Elastomeric materials having a high hardblock content and process for preparing them
US8349908B2 (en) 2008-03-07 2013-01-08 Huntsman International Llc Foamed materials comprising a matrix having a high highblock content and process for preparing them
US9259515B2 (en) 2008-04-10 2016-02-16 Abbott Cardiovascular Systems Inc. Implantable medical devices fabricated from polyurethanes with grafted radiopaque groups
AU2010330056B2 (en) * 2009-12-11 2015-03-26 Basf Se Improved porous materials based on aromatic amines
EP2399945A1 (de) * 2010-06-28 2011-12-28 Basf Se Verfahren zur Herstellung von Porösen materialien auf basis von Polyharnstoff
DE102011002809A1 (de) * 2011-01-18 2012-07-19 Henkel Ag & Co. Kgaa 2K-PU-Zusammensetzung mit verzögerter Vernetzung
EP2808353A1 (de) * 2013-05-31 2014-12-03 Huntsman International Llc Verfahren zur Verbesserung der Festigkeit von Polyisocyanat-Polyadditionsreaktionsprodukten
EP3063199B1 (de) * 2013-10-30 2020-07-01 Dow Global Technologies LLC Syntaktische polyurethanelastomere mit unterschiedlicher morphologie zur verwendung in unterwasserrohrleitungsisolierung
CN105637006B (zh) * 2013-10-30 2019-08-30 陶氏环球技术有限责任公司 用于海底管道保温的复合聚氨酯弹性体
DK3063198T3 (da) * 2013-10-30 2019-11-11 Dow Global Technologies Llc Syntaktiske polyurethanelastomerer baseret på polyoler med lav umættethed til anvendelse til isolering af undervandsrør
SG11201603249UA (en) * 2013-10-30 2016-05-30 Dow Global Technologies Llc Syntactic polyurethane elastomer based on soft segment prepolymer and non-mercury catalyst for use in subsea pipeline insulation
US10316132B2 (en) * 2014-09-04 2019-06-11 Dow Global Technologies Llc Polyurethane mats
PL3645593T3 (pl) 2017-06-27 2023-10-23 Basf Se Miękkie pianki poliuretanowe o polepszonej przepuszczalności powietrza
CN108084394B (zh) * 2017-12-25 2020-09-29 青岛科技大学 一种形状记忆硬质聚氨酯发泡医用夹板材料及其制备方法
EP4010414A1 (de) * 2019-08-08 2022-06-15 Recticel Verbessertes verfahren zur wiederverwertung von polyurethanwerkstoffen
US11732083B2 (en) 2020-11-19 2023-08-22 Covestro Llc Polyisocyanate resins

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2083484B (en) * 1980-09-10 1983-12-21 Texaco Development Corp Reinforced reaction injection molded elastometers
US4444703A (en) * 1980-09-10 1984-04-24 Texaco Inc. Reinforced reaction injection molded elastomers
US4686240A (en) 1985-10-25 1987-08-11 Union Carbide Corporation Process for producing polyurethane foams using foam modifiers
GB8712988D0 (en) 1987-06-03 1987-07-08 Ici Plc Polyurethane foams
US4822827A (en) * 1987-12-17 1989-04-18 The Dow Chemical Company Thermoplastic polyurethanes with high glass transition temperatures
US5061254A (en) * 1989-06-21 1991-10-29 Becton, Dickinson And Company Thermoplastic elastomeric hydrophilic polyetherurethane expandable catheter
US5418261A (en) * 1993-01-25 1995-05-23 Imperial Chemical Industries Plc Polyurethane foams
GB9301428D0 (en) * 1993-01-25 1993-03-17 Ici Plc Polyurethane foams
CN1039423C (zh) 1993-04-13 1998-08-05 帝国化学工业公司 软质泡沫塑料的制备方法
US5773483A (en) * 1993-04-13 1998-06-30 Imperial Chemical Industries Plc Process for preparing a flexible foam
US5418260A (en) * 1993-10-04 1995-05-23 Ecp Enichem Polimeri Netherlands, B.V. Process for the production of polyurethane articles from uretonimine based compositions and ethylene oxide rich polyether polyols
EP0778855B1 (de) * 1994-09-01 1999-06-16 W.L. Gore & Associates, Inc. Hydrophyles polyurethan
US5627254A (en) * 1996-05-03 1997-05-06 The Dow Chemical Company Rigid thermoplastic plyurethane comprising units of butane diol and a polyethylene glycol
PL188405B1 (pl) * 1996-06-27 2005-01-31 Huntsman Int Llc Sposób wytwarzania mikrokomórkowej elastomerycznej pianki poliuretanowej
EP0937114B1 (de) * 1996-11-08 2002-08-14 Huntsman International Llc Verfahren zur herstellung von polyurethanhart- und weichschäumen
US6031010A (en) * 1997-08-11 2000-02-29 Imperial Chemical Industries Plc Polyurethane foam composition having improved flex fatigue
ES2218149T3 (es) 1999-03-17 2004-11-16 Huntsman International Llc Procedimiento para la preparacion de material de poliuretano moldeado.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3898745B1 (de) * 2018-12-19 2023-08-30 Basf Se Polyurethan-weichschäume mit verbesserten dauergebrauchseigenschaften

Also Published As

Publication number Publication date
ES2247161T3 (es) 2006-03-01
CN100369948C (zh) 2008-02-20
CA2417267A1 (en) 2002-02-07
ATE308576T1 (de) 2005-11-15
AU2001285777B2 (en) 2005-08-04
BR0112898A (pt) 2003-06-10
CZ298395B6 (cs) 2007-09-19
AU8577701A (en) 2002-02-13
DE60114633D1 (de) 2005-12-08
SI1305354T1 (sl) 2006-02-28
US20030130470A1 (en) 2003-07-10
CA2417267C (en) 2009-04-14
DE60114633T2 (de) 2006-07-20
AR030089A1 (es) 2003-08-13
EP1178063A1 (de) 2002-02-06
ZA200300295B (en) 2003-11-07
CN1446238A (zh) 2003-10-01
RU2268270C2 (ru) 2006-01-20
BR0112898B1 (pt) 2010-12-14
WO2002010249A1 (en) 2002-02-07
PL365156A1 (en) 2004-12-27
US6806342B2 (en) 2004-10-19
MXPA03000667A (es) 2003-06-04
JP4953544B2 (ja) 2012-06-13
KR100730670B1 (ko) 2007-06-21
JP2004505142A (ja) 2004-02-19
EP1305354A1 (de) 2003-05-02
CZ2003257A3 (cs) 2003-05-14
TWI257934B (en) 2006-07-11
KR20030064740A (ko) 2003-08-02

Similar Documents

Publication Publication Date Title
EP1305354B1 (de) Verfahren zur herstellung eines polyurethanmaterials
EP1303551B1 (de) Verfahren zum herstellen eines elastomeren
AU2001285777A1 (en) Process for preparing a polyurethane material
EP1940898B1 (de) Verfahren zur herstellung eines polyisocyanuratpolyurethanmaterials
US8785570B2 (en) Process for preparing a polyisocyanurate polyurethane material
CA2523481C (en) Process for preparing a polyisocyanurate polyurethane material
EP1263831B1 (de) Verfahren zur herstellung eines flexiblen polyurethanschaums
AU2001266090A1 (en) Process for preparing an elastomer
EP1234843A1 (de) Verfahren zur Herstellung von Polyurethanweichschaum
US20030060528A1 (en) Process for preparing a flexible polyurethane foam
EP1174453A1 (de) Verfahren zur Herstellung eines flexiblen Polyurethanschaumes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030113

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: SI

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60114633

Country of ref document: DE

Date of ref document: 20051208

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060202

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060202

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2247161

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060630

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20090611

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20090605

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090710

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20100513

Year of fee payment: 10

Ref country code: FI

Payment date: 20100607

Year of fee payment: 10

Ref country code: PT

Payment date: 20100510

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20100507

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20100518

Year of fee payment: 10

BERE Be: lapsed

Owner name: *HUNTSMAN INTERNATIONAL LLC

Effective date: 20100630

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20110101

EUG Se: european patent has lapsed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20111226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111226

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110625

REG Reference to a national code

Ref country code: SI

Ref legal event code: KO00

Effective date: 20120130

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 308576

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110625

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110625

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20140606

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20150526

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20150611

Year of fee payment: 15

Ref country code: FR

Payment date: 20150528

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150630

Year of fee payment: 15

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160727

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150626

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60114633

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20160625

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160630

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160625